Process and apparatus for contacting fluids



July 27, 1937. s. 'nJMsTRA l PROCESS AND APPARATUS FOR CONTACTING FLUIDS Filed Dec. 4, 1934 Patented July 27, 1937- PRD'CESS ANI) APPARATUS' FOR' CONTACT- .Y ING FLUIDS Sijbren Tijmstra., Berkeley, Calif., assignor to Shell ADevelopment Company, San Francisco, Calif.,` a corporation of Delaware Application December 4, 1934, Serial No. '155,871

`'z claims.- (c1. 19e-13) This invention relates to the art of contacting two liquids for the purpose of achieving al chemical or physical interaction between them. My improved process and apparatus may be used f with advantage in connection with any process of installation which involves the countercurrent ilow of two liquids or liquid phases.` Examples of such processes are the solvent extraction` of liquid mixtures, such as hydrocarbon mixtures, mixtures of organic acids and water, and other mixtures or'solutions; the acid treatment of mineral oils or other liquids; the neutralization of solutions, etc. v

It is an object of my invention to provide an improved process and apparatus for contacting two liquids flowing countercurrently through a zone provided with contact means, in which chanr neling will be avoided or reduced, and/or in which the two liquidsare'brought intomore intimate. j contact than has been possible with the known processes. It is a further object of my invention to provide an apparatus which will be automatic in operation and which will be economical to operate. 3; apparent from a reading of the specification.

Ithis known to contact the liquids by introducing them atv vertically spaced points of a column or tower, and withdrawing the products at other vertically spaced points. With a view 30 of obtaining a better contact between the two liquids it has been proposed to provide the tower with contact means. The disadvantage of such an installation, however, is that channeling is vlikely tn occur. In this condition one liquid or 23 phase ows upwardly in small streams in certain parts of the tower, and the other liquid or phase flows downwardly in similar streams, but in other parts of the tower; thereby preventing effective contact between'them. 10 I have found that in contacting liquids in a chamber provided with contact means, channeling can be prevented and that the liquids can be brought into much more effective contact by passing a gas upwardly through all or a part of 4" the length of a substantially-vertical tower. 'It

is an essential feature of my improved process that thegas agitates the liquids orA phases while they flow countercurrently in a contact zone 50 which has' been provided with suitable contact.

means. By the term contact zone I mean the space within a column or other containerin which the `two liquids orphases of differing specic gravity ow countercurrently while-in inti- 55 mate contact with each other. The contact Other objects of my invention will be means may consist of any suitable packing material, as described below, or a Aseries of perforated plates which will aid in bringing the twoV liquids into eifective contact. The settling zone may consist of a single column or tank, or of a series of such apparatus.

In this specification and drawing,lI have illus- I trated three forms of apparatus which are suitable for carrying out my process, but it is to be understood that the invention-is not limited to such forms, because itmay be embodied in other forms which will be apparent to thoseskilled in the art.

In the drawing, Figure I is a longitudinal sectional view ot one preferred embodiment of the apparatus; Figure l1 isa fragmentary view,`

similar to-Figure I, showing a modied form of the apparatus;v and Figure III is an elevation, partly in s ection, showing a modified level control arrangement. For convenience, I shall describe my invention in relation to a solvent ex-4 traction system, but it is to be understood that it may be applied to other liquid cpntact treat-y ments. i,

Referring toFigure I of the drawing, the liquids to be contactdare introduced through inlets l and 2, controlled by valves 3and 4 respecti ly, into a packed tower. I Suitable spiders or ozzles may be provided to distribute the liquids in the tower. The' tower 5 may be lled in its lower part with relatively small packing material 6, and at'itsupper part with larger packing material 1. According` to one embodiment of 4my invention the lower'portion of the'tower may be packed with small balls, and the upper portion with larger rings. I may, however, substitute therefor any suitable contact means, such as perforated rings, plates or discs, Raschig rings, coke, pebbles, or any honeycombed, perforated or porous material.` A gas, preferably one which is inert in relation to the liquids in the tower, flows througha pipe 8 and valve 9 into a constant pressure storage tank l0. The gas enters the contact apparatus through' a check valve Il, conduit l 12, pump I3, and is discharged through a nozzle I4, located at any desired point in the tower.

The heavier phase produced in the column 5,

ows downwardly through the packing 6 and 1,

and the lighter phase flows upwardly, countercurrently to and in intimate contact with theA This turbulence 4 tive movement of the two liquid phases. Its rate must, however, be regulated, because an excessive ow of gas may entirely prevent the countercurrent movement.

Although it is possible to pack the tower so as to cause the packing material to rest directly on the bottom 5, I prefer to arrange the packing in a manner to provide an unobstructed settling zone I6 near the bottom of the column. This may be accomplished by supporting the packing material 6 on a perforated plate I1.

The heavier phase produced in the column ilows downwardly through the packing and accumulates in the settling zone I6, which is free from turbulence. In this quiescent zone, the entrained drops of the lighter phase coalesce and flowupwardly, thereby causing stratiiication. Theliquid above the interphase I8, will be a mixture of the heavier extract Iphase and of the lighter phase, while the liquid below this interphase will consist substantially of pure 'extract phase, which is withdrawn through an outlet I9. To insure the withdrawal of extract phase ofthe desired composition a float 20, designed to rise and fall with the interphase I8 is arranged to control throttle valve 2| by means of a valve actuating system 22.

The lighter phase and the gas which rise in the column are in a state of turbulence;` they form a mixture which usually contains a certain quantity of entrained heavier liquid which should form a. part of the heavier phase. This turbulent mixture is guided by the truncated conical baflies 23 and 24 into a cylindrical chimney 25, which is surrounded by a cylindrical baille 2B, extending at least as far down as the upper edge of the chimney 25. 'I'his `arrangement permits the gas to rise inside of the baliie 26 to the` top of the column 5, whereit is withdrawn through an outlet 21. At the same time it permits the liquids to enter a quiescent annular settling zone 28 where the phases may stratify, producing an, interphase 29. The liquid phase below this interphase contains heavier components of the system, and ows back into the extraction zone through an annular opening 30. The liquid above interphase 29 consists of the lighter phase of the system, and is withdrawn through an outlet 3|, regulated by a throttlevalve 32. This valve is actuated by the valve actuating System 33 and controlled by theoat 34, which floats on the surface of the liquid in the column.

The gas may be freed from entrained liquid by means of bailies 35, or it may be passed through an outside liquidseparator. A safety pressure relief valve 36 maybe provided. The gas ilows through a conduit 31, Aand. is re-introduced atw|4 by means of the pump I3.

The system may be operated at any desired pressure, either above or below atmospheric The operating pressure is determined by the pressure in the reservoir l0, in the following manner: In the course of the operation certain amounts of gas are lost by being dissolved or en- The time required for proper stratification of the liquids in the settling zone 28 will frequently be so great as to require an excessively large settling Zone. It will in these situations be more feasible to provide an auxiliary settling chamber, which may be of any desired size, not dependent- Y upon the cross section of the columnV 5, andwhichmay also 'serve as a gas separator. Such a construction isindicated in Figure II, showing the upper portion of a modified column |05, provided with a gas outlet |21, relief valve |36, and liquid outlet |3I. A baiile |38 may be arranged in the column so as to prevent the vwithdrawal of substantial amounts of gas through the outlet |3I. The light phase, containing certain amounts of entrained gas and heavier liquid, is introduced into a settling apparatus |39, which is free from turbulence,- and permits gas to leave the liquid. The entrained heavier phase settles below the interphase |29 and is returned to the column |05 by a conduit I 40. The light phase is Withdrawn through a conduit MI which is regulated by a throttle valve |32, actuated by a valve actuating system |33 and controlled by a float |34, which may be located either in the apparatus |39 or in the column |05. The gas withdrawn at |21 may, likewise, be introduced into the apparatus |39, and be freed from entrained liquid by passing between bafiles |35, and be Withdrawn through an outlet |31.

Figure III illustrates a modified arrangement of the liquid and gas valves, whereby the level of the liquid is controlled in a novel manner. The extraction column 205, inlets 20| and 202, outlets 2I9, 221 and 23|, valves 22| and 236, and pump 2 I3 are similar to thecorresponding elements described in connection with Figure I, and bearing corresponding reference characters. The rate at which the liquid is discharged from the outlet 23| will depend upon the pressurewithin the column by means of the valve actuating system 233. An

auxiliary solvent may be introduced through inlet245.

Y Many applications-of my process for contacting two substances will be apparent to those skilled in the art, and I am not thus limited to any particular use of my process, altliough a few examples of its application will be given. For example, the apparatus and process find utility in the treatment of petroleum and its products with sulfln'ic acid. In this operation sulfuric acid is introduced through the inlet I, and a petroleum fraction, such as gasoline, kerosene, gas oil, lubricating oil, etc., is introduced through the in'- let 2. An inertgas, preferably nitrogen, is introduced through the inlet 8,- and the nozzle I4. 'Ihe spent acid and treated mineral oil fraction are withdrawn-through the outlets I9 and 3|, respectively. Furthermore, a liquid or solution may be eiectivelywashed by the use of my Cil process and apparatus. Examples of this type are numerous, and include the washing of a liquid with an alkali solution after acid treatment of ammoniacal liquor, the-washing of oils to free them of phenols, etc.

My invention ilnds especial application in the art of extracting liquid mixtures with selective solvents. For example, hydrocarbon oils may be' -extracted in accordance with my invention.

remove naphthenic and aromatic components therefrom, the-oil is caused to liiow countercurrently to a suitable selective solvent, such as liquid sulfur dioxide, Chlorex or dichlorethyl ether, furfural,'phenol, nitrcbenzene, quinoline, isoquinoline, alcohol, diacetone alcohol, etc., yor solvent mixtures, thereby producing raflinate and extract phases, which are removed at oppouse of an auxiliary solvent having a favorable effect in the distribution of oil components in extract and raiiinate phases may under certain conditions be desirable. When used, it may be introduced into the tower near the point at which the extract phase is withdrawn. An inlet 45 controlled by a valve 46 may be used for this purpose. In the extraction of lubricating oils,` light `naphthas, gasoline or kerosene are suitable auxiliary solvents..

Instead, a backwash .consisting of the nal extract may also be used. In any of these modes of operation, the gas, which may, for example, be nitrogen, produces a better contact and prevents channeling.

The'improved results are apparent from the following example:

The lower two-thirds of a Vertical tower having a diameter of 11/2 inches and a height ofv 9 feet was lled with 4 mm. diameter glass beads, 'and the remainder with 6 mm. diameter glass rings.' A selective solvent mixture consisting of 3 parts of furfural and 1 part of benzol was introduced at the top of the tower and an lauxiliary solvent, consisting of isopentane, was introduced lat the lower end of the tower. Oil was introduced at a point about 3 feet from the bottom. In experiment l, nitrogen was introduced at the bottom of the tower at a rate suicient to cause the required turbulence, but not suflicient to prevent the countercurrent ow o f the liquid phases. In

experiment 2, no 'gas was used. The data oi' the two experiments are. tabulated below:

From the tabulation it is evident that the introduction of gas caused better contact between the two liquid phases and that due to the increased eiiciency of the extraction a higher yield of theA same quality of rafiinatewas produced with the consumption of less than half the amount of solvent-required for the experiment which omitted Athe use of gas.

Numerous modications of my apparatus to meet specific conditions will be apparent to those skilled in the art. Thus, the .valve control systems may be operated electrically, instead of by the iloats shown. The inlet 45 could, similarly, be located so as to introduce the auxiliary solvent at a. point below the interphase I8.

'I'he tower may, further, be provided with coils or a jacket for providing a gradual temperature gradient. from a low temperature near the extract phase outlet to a higher temperature at the opposite end of the zone, thereby further improving the extraction emciency. 'I'his feature isknown in the extraction art and a further detailed description is unnecessary.

I may further use the gas to control the temperature in the tower byintroducing va refrigerant heat exchanger 41.

As used in the present specication and claims the term solvent is intended to include solvent mixtures. The term component is not 'lim'- ited to pure substances, but is intended to include groups of substances which exhibit similar properties in relation to a selective solvent. 'I'here is no diierence between the terms liquid, liquid mixture and solution,

I claim as my invention: 1. The process for bringing two at leastpartially immiscible liquidsof diierent specific gravities into intimate contact which comprises:.

iiowing the heavier liquid downwardly in a contact zone of a contact tower through contact means, flowing the lighter liquid upwardly through said contact means thereby producing heavy and light liquid phases, introducing a current of inert gas near the lower end of said contact zone in a quantity suicient to cause effective turbulence in said'zone but not sufficient to preventcountercurrent movement of the liquids,

-withdrawing the heavier phase near the lower phase in quantities to maintain the level of the liquid at a predetermined level below the top of the tower, withdrawing the gas at the upper end of the tower, recirculating at least a portion of the gas into the lower end of said zone through a gas conduit means and admitting additional gas at a constant pressure into the gas conduit means so as to` maintain a substantially constant pres` sure at the top of said contact tower.

2. The process for bringing two at least partially immiscibleliquids of different specic gravities into intimate contact which comprises: loW- ing the heavier liquid downwardly in a. contact zone o f a contact tower through contact'means,

iiowing the lighter liquid upwardly through said contact means thereby producing heavy and light liquid phases, introducing a current of inert gas near the lower end of said contact zone in a quantity suilicient to cause eiiective turbulence in said zone but not sufficient to prevent countercurrent movementof the liquids, withdrawing the heavier phase near the lower end of said tower, withdrawing the lighter liquid near the upper end of the tower in response to the pressure prevailing within said tower, withdrawing the gas at `the upper end of, said tower, recirculating atleast additional gas into the tower when the liquid is above a desired level, and admitting less additional gas when the liquid is below a desired level.

3. In combination, a countercurrent treating apparatus comprising a contact zone, means within said zone for aiding the contacting of liquids, a first inlet means for introducing liquid near one end of the zone, a second inlet means forintroducing a second liquid at a point in said zone removed from said rst inlet means, a gas nozzle in said zone located in substantial spaced relation to the topv of said zone, pump and conduit means for supplying gas under pressuret0 said gas nozzle, outlet me an's near opposite ends of said apparatus for withdrawing liquid phases from said apparatus, the upper outlet means being spaced from the top of the apparatus, a throttling valve in the said upper opening, a oat controlled means for actuating said valve to maintain the liquid in the apparatus at a predetermined level below the top of said apparatus and above the said upper liquid outlet means, an.

outlet means at the top of said apparatus for withdrawing gas from the top of the apparatus, conduit means for conducting withdrawn gas fromv the top of the apparatus to the pump, a source of gas under constantpressure, and valve and vconduitmeans arranged to admit gas from said source to .the said pump and conduit means when the pressure in the latter falls below apredetermined value. l

4. In combination, a countercurrent treating apparatus,` comprising a-contact zone, means within said zone for aiding the contacting of liquids, means for introducing a liquid near one end of the'zone, means for introducing a second liquid at an intermediate point of the zone, a gas nozzle in the zone in substantial spaced relation 'to the top of the zone, a source of gas, valve v means for. regulating'the supply of gas, pump and conduitmeans connecting -said nozzle and valve means for supplying gas to said nozzle, a

iirst outlet means near the lower end of the apparatus for withdrawing a heavier liquid phase, a second outlet meansnear the top of said apparatus for withdrawing the lighter liquid phase from the apparatus, outlet means in the top of the apparatus for withdrawing gas from the apparatus, conduit means for conducting said gas from the top of the apparatus to the conduit between the pump and the said valve means, a float arranged to move in response to theV surface of the liquid in the apparatus, and float controlled valve actuating means arranged to admit addi-- tional gas from said source when the liquid rises above a predetermined level between the top of said apparatus and the second outlet means, and

to admit less gas when the liquid falls below said level.

5. In a countercurrent treating apparatus, a tower comprising a contact zone, means within said zone for aiding the contacting of liquids, means for introducing a liquid near one end of the zone, means for introducing -a second liquid at an intermediate point of the zone, a gas nozzle in the zone in substantial spaced relation to the t'p of the zone, a source o! gas, valve means for regulating the supply of gas, pump and conduit means connecting said nozzle and valve means for supplying .gasto said nozzle, a rst outlet means near the lower end of the zone for withdrawing a heavierliquid phase, a phase separator, a second outletmeans near the top of said zone for withdrawing the lighter liquid phase .from the zoneand conductingvit to the intermediate sectiony of the separator, means for :withdrawing liquidffrom the separator, outlet means in the top. oi? the separatorfor withdrawing liquidgfreed gasirom; thefseparator, conduit' means for conducting said Agas from the separator' to the conduit .between the pump and the saidl valve means, afloat arranged to move -in response to the surface of the .liquid in saidseparator, and oat controlled valve actuating means arranged to admit additional gas from said source when Athe liquid rises abovea predetermined level between the top of said separator and the liquid`outlet means in the separator, and to admit less gaswhentheliquid ialls below said level.l f

6. Countercurrent treating apparatus comprising a contact zone, means within said zone for aidingthe contacting of liquids, means for introducing a liquid near one end of the zone,

means for introducing a secondliquid at an in.

termediate point of said zone, afgas nozzle in the zone in-substantial spaced relation to the top of said zone, a source of gas, valve means for regulating the supply of gas; pump and conduit means connecting said nozzle'and' valve means `for supplying gas to said gasnozzle, a rst settling zone below and in direct communication -with saidV contact zone, an outlet near the bottom of said rstsettling zone 'for withdrawing a heavier liquid phase, a second settling zone above said contact zone, baille means arranged to cause sub'- stantially only liquid from the contact zone to enter the secondvsettling zone at an intermediate level thereof, gas outlet means for said contact zone and for said second settling zone, an outlet -near the top of said second settling zone and below the top of the liquidlevel for withdrawing Va' lighter phase, and means for returning a heavier phase -from the lower portion of said second settling zone into said contact zone. Y

7. The process f'or bringing two at least partially immiscibie liquids vof diiferent specic gravities into intimate contact which comprises: introducing the heavier and light liquids near the top and n ear the bottom, respectively, of a contactzone which is packed with means for aiding the contact of said liquids, 'maintaining the conditions of flow of the two liquids through the zone' such as would cause channeling without .gas agitation, introducing a current of inert gas near the lower end of said zone in a quantity sufficient to cause effective turbulence in said zone suilicient to prevent channeling but not sufficient to prevent. countercurrent flow of the two liquids,

removing gas from the upper portion of said zone, and removing the contacted liquids at opposite ends of the zone. 

